High temperature erosion resistant coating and material containing compacted hollow geometric shapes

ABSTRACT

A method for making a material system includes the steps of: providing a chamber, placing hollow geometric shapes in the chamber, closing the chamber, evacuating air from the chamber, feeding a binder for the shapes into the evacuated chamber to impregnate the geometric shapes, drying the binder permeated geometric shapes, and heating the hollow shapes and binder to provide a unitary, sintered material system.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of making high temperature,erosion resistant coatings used as abradable seals and thermal barriercoatings.

2. Background Information

Most components of combustion turbines are operated at very hightemperatures and often require the use of specialized coatings/insertsto protect underlying supporting materials. These specializedcoating/inserts include thermal barrier coatings (TBCs), turbine bladetip inserts, and abradable seals disposed opposite the turbine bladetips, as taught in U.S. Pat. No. 5,180,285 (Lau).

Conventional TBCs typically comprise a thin layer of zirconia. In manyapplications, the coatings must be erosion resistant and must also beabradable. For example, turbine ring seal segments, which fit with tighttolerances against the tips of turbine blades, must withstand erosionand must preferentially wear or abrade in order to reduce damage to theturbine blades, and form a tight seal with the turbine blade. Protectivecoating system can include several layers including a metallic bond orbarrier coating of MCrAlY having an alumina scale and, for example, acolumnar yttria stabilized zirconia thermal barrier, as taught in U.S.Pat. No. 4,916,022 (Solfest et al.), which can be further coated by anerosion resistant layer of alumina or silicon carbide, applied byphysical vapor deposition techniques, as taught by U.S. Pat. No.5,683,825 (Bruce et al.).

In U.S. Pat. No. 5,780,146 (Mason et al.), 30 wt. % to 50 wt. % (50 vol.% to 60 vol. %) of hollow alumino silicate or alumina spheres of 400micrometer to 1800 micrometer diameter, and having a high temperaturecapability of approximately 1300° C., were used in an aluminum phosphatematrix, for an abradable seal. The seal is used over a ceramic matrixcomposite shroud segment, which may comprise silicon carbide fibers inan alumina matrix. There hollow spheres were mixed with an aluminumphosphate paste to form a sliarry, followed by molding to the requiredshape.

Fillers have also been used by Naik et al., in U.S. Pat. No. 5,064,727.There, abradable stationary seal walls, for jet turbine housings whichseal opposing, rotating rotor blade tips, have a ceramic core containingfrom 30 vol. % to 98 vol. % solid ceramic filler, where the ceramicfills a honeycomb wall structure. This is then covered with erosion andcorrosion resistant outer layer, which is made porous by uniformlydispersed, finely divided filler. This is apparently applied by aspraying technique. The pores can be filled with ceramic, metal oxide orcarbide materials. Fillers mentioned include hollow ZrO₂.8YO₃ ceramicspheres and solid Al₂O₃,SiC,TiC and BN spheres.

Other abradable honeycomb structures for use in turbines are taught inU.S. Pat. No. 4,867,639 (Strangman). There, low melting fluorides, suchas BaF₂, are incorporated into a stabilized zirconia or alumina matrixwhich, in turn, is used to fill a honeycomb shroud lining made of, forexample, a metal alloy. The filling becomes molten when the rotatingblade tips rub the shroud, and upon resolidification, improve thesmoothness of the abraded surface. Ainsworth et al., in U.S. Pat. No.4,639,388, teaches another variation of reinforced ceramic layers,including a honeycomb matrix for use in a turbine as abradable seals.

In U.S. patent application Ser. No. 09/261,721 (RDM 97-017, Merrill etal., filed on Mar. 3, 1999), a honeycomb structure having open cells wasfilled, and optionally overlayed, with a material containing hollowceramic particles embedded in an interconnected ceramic matrix, toprovide a composite thermal barrier coating system having superiorerosion resistance and abrasion properties for use on combustion turbinecomponents. The hollow particles were preferably spherical and made ofzirconia, alumina, mullite, ceria, YAG or the like, having an averageparticle size of about 200 micrometers (0.2 mm) to 1500 micrometers (1.5mm). The steady state erosion rate, grams lost/kg erosive impactingmedia, of this filler was 3.2 g/kg vs. 4.6 to 8.6 g/kg for conventionalTBCs. Here, the ceramic matrix comprised an interconnected skeletonbinding the hollow spheres together where the hollow spheres were bondedby a network of aluminum phosphate bridging bonds. The matrix wasapplied as a slurry mixture of hollow particles, filler and binder,which was heated within the honeycomb structure to form a packedinterconnecting ceramic matrix with embedded hollow particles. Theflowable ceramic filler material was preferably packed into the opencells of the honeycomb using a combination of agitation and manuallyassisted packing using pushrods or tamping brushes to force pack thehollow spheres into the honeycomb cells ensuring complete filling.Alternate packing methods such as vacuum infiltration, metered doctorblading and similar high volume production methods were also mentioned.

In U.S. patent application Ser. No. 09/267,237 (99E9112US, Merrill etal., filed on Dec. 20, 1999), a material system useful as an erosionresistant layer for turbine applications was described. There, closelypacked hollow, geometric shapes, such as hollow spheres were mixed withbinder and other particles and bonded together with a matrix material toprovide abradable, porous, thermally stable seals, and the like.

However, none of these coatings or seal structures have optimizedabradability with erosion resistance and insulating capability,minimized shrinkability and thermal mismatch, provided constrainedstabilized porosity and adequate flexibility, and optimized thermalstability at over 1600° C.; all of which characteristics are required ofthe next generation high temperature turbine TBCs, blade tip coatingsand seals. What is needed is a method of making high temperature turbinecoatings and composites that fill these requirements.

The present invention has been developed in view of the foregoing, andto address other deficiencies of the prior art.

Therefore, it is one of the main objects of this invention to provide amethod making a high temperature, erosion resistant coating and materialwhich is bondable, non-shrinking, abradable, flexible, thermally stableup to at least 1600° C., and which has constrained stabilized porosityand insulating properties, as well as controlled thermal conductivityand thermal expansion properties.

SUMMARY OF THE INVENTION

These and other objects of the invention are accomplished by providingmethod of making a material system, useful as an erosion resistant hightemperature layer, comprising the steps: (1) providing a chamber havingtop, bottom and side surfaces, (2) opening the chamber and: filling thebottom chamber with a plurality of generally to contacting, hollowgeometric shapes having a dense wall structure, such that the shapes areclose packed with void spaces therebetween and so that a substantialnumber of the shapes contact at least 1 adjacent other shape, to providea packed array in the chamber, and feeding a binder material into thechamber so that before drying in step (3) the binder permeates andpenetrates to the void spaces, coating the hollow geometric shapes andimpregnating and filling substantially all empty space within thechamber (3) drying the binder permeated packed array to form a greenmaterial system binding coating on walls of the hollow shapes and withinsubstantially all the void spaces, (4) heating the dried, binderpermeated packed array at a temperature and for a time effective tosinter the hollow shapes and binder together to provide a unitary,sintered material system.

This sintered material system can be used alone as a coating or can beapplied to a substrate to form a composite. The sintered material systemcan again be subjected to further impregnation. Preferably, step (2)involves filling the chamber with the shapes (2a), followed by steps(2b) closing the chamber, and (2c) applying a vacuum within the chamberto withdraw air from the void spaces, where feeding the binder materialbecomes step (2d).

The binder material can be a binder solution or a slurry of binder andultra fine hollow or solid shapes effective to substantially fill thevoid spaces. Usually, the hollow geometric shapes are hollow ceramicspheres made, for example, of mullite and the like, and the bindermaterial can be, for example, an aluminum phosphate solution.

Preferably, this process first packs the hollow shapes so that there issubstantial contact and substantial chains of contacting shapes, andthen diffuses a binder through the contacting shapes. This provides amaterial system having a bonded compacted chain structure of hollowshapes, resulting in a constrained stabilized uniform sphericalporosity, having thermal stability and non-shrinking properties at up toa temperature of at least 1600° C. This process allows intimate chainpacking not attainable by plasma spraying or other type coating of ahomogeneously mixed filler binder composition, and provides forindividually formed rather than in-situ formed hollow shapes, allowingcontrol of wall thickness and density of the hollow shape. This methodprovides a strong yet porous mass with an optimized combination ofphysical and thermal properties needed in the industry but heretoforenot attainable.

Preferably, the geometric shapes are selected from rigid, hollow,essentially closed ceramic spheres and other similar geometric shapes oflow aspect ratio, less than 10 and preferably less than 5, such ashollow cylinders and the like. The shapes are “individually formed,”defined here as formed separately and stabilized, rather than beingformed in situ on a substrate etc. The hollow ceramic shapes have“dense” walls, defined here as having a density from 90% to 100% oftheoretical (0% to 10% porous). Because the geometric shapes areindependently formed, denser wall formation results, which allows crackdeflection and general toughening of the material, as well as allowingstabilization to very high temperatures approaching 1700° C. Hollowspaces between, for example, one diameter of the large geometric shapescan be filled with smaller diameter geometric shapes, to reduce voidvolume and minimize, consistent with some measure of flexibility, thecontent of matrix ceramic bonds which help bond the shapes together.

Preferably, there are three dimensional “chains” of hollow shapes, wherea substantial number of shapes contact at least 4 to 12, preferably 6 to10, other shapes. This chain or string-like geometry provides strengthand minimizes large void volumes being close to each other. The materialsystem should have some measure of porousness, at least 15 vol. %usually up to a maximum 90 vol. %, preferably 40 vol. % to 70 vol. % forturbine thermal insulating and abradable coatings, and preferably hassome randomness of the contacting shapes in its structure. The method ofthis invention allows such porous shapes having chain structures which,when sintered, are highly friable, while maintaining a low elasticmodulus.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is further illustrated by the following non-limitingdrawings, in which:

FIG. 1 is a cross-section through a gas turbine shroud and other turbinecomponents in a turbine assembly, showing an abradable seal and aturbine tip, with associated turbine blades and vanes;

FIG. 2 is a generalized drawing of what one embodiment of the filled,abradable structure made according to the method of this invention,containing about 30 vol. % to 60 vol. % of generally contacting spheres,having coordination numbers of about 3 or 4 to 6, might ideally looklike on a microscopic level;

FIG. 3 is a generalized drawing of what the filled, abradable structuremade according to the method of this invention containing about 50 vol.% to 90 vol. % of generally contacting, substantially close packedspheres, having coordination numbers of about 5 to 12, might ideallylook like on a microscopic level;

FIG. 4 is an idealized, enlarged view of one part of one layer of thegenerally contacting close packed structure of FIG. 3, but with lowercoordination numbers of from about 6 to 10, and containing hollowspheres;

FIG. 5, which best shows the invention, is a block diagram of the methodof this invention; and

FIG. 6 is a schematic diagram of one embodiment of the vacuum/packingmold that can be used in the method of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring now to FIG. 1, a combination of rotatable turbine blades 12and stationary turbine vanes 14 are shown in a turbine assemblyapparatus 10 having a turbine casing 16. Turbine shrouds 18 are arrangedcircumferentially around one of the stages of the turbine blades andhave abradable shroud seal layers 20 which cooperate with the turbineblade tip layer inserts 22 to form a seal area 24, shown wide for thesake of clarity. Blade attachment root 26 is also shown as well assupport plate substrate 28 for the seals 20 and potential thermalbarrier layer 25 on the turbine blade 12. The vanes 14 are stationaryand confine and guide hot gases flowing through the associated gasturbine. Thermal barrier layer 25 could also be used on the vanesurfaces. The layer 25 is only shown on the edge but can and usuallywould cover the entire surface of the blade 12 and vane 14.

In order to improve performance (thermodynamic efficiency and poweroutput), thermal barrier layers have been applied to cooled turbinecomponents to reduce the amount of cooling air, etc., required.Recently, to improve efficiency, the seal leakage area 24 has beenreduced by having the blade tip insert 22 contact and abrade the shroudseal 22, to provide individual, tight seals between each seal and itscorresponding turbine blade. In this invention the shroud seal, theblade tip insert and most other seal or wear areas in the turbineapparatus can be made of an erosion resistant, filled, high temperaturematerial, made by the method of this invention, utilizing from about 20vol. % to 85 vol. % of hollow geometric shapes having walls over 70%dense. These same coatings are also useful as a thermal barrier coatingfor blades, vanes, combustors and other like objects in a gas turbineengine which currently require active cooling.

In FIGS. 2 and 3 the spheres used in the method of this invention areshown as three dimensional bodies, but it is understood that they arehollow shapes, more clearly shown in FIG. 4. Referring to FIG. 2, oneexample of a material made by the method of this invention is ideallyshown as 32, in idealized form, as a segment within the dotted lines.First layer with spheres A is somewhat discontinuous, although mostspheres contact at least two other spheres, with a substantial number,that is about 70% contacting three other spheres, which is apparent inlocations where the second layer spheres B are shown. Second layerspheres, B are also discontinuous, but with substantial contact withfirst layer spheres. Only one-third layer, black sphere C is shown forthe sake of clarity. The matrix spaces 34 provide moderate porosity inaddition to the closed porosity inherent within the hollow geometricshapes. This interstitial porosity is of secondary importance to theoverall wear and thermal properties of the structure, but can becritical to the mechanical behavior—especially at the higher porosityrange. The erosion performance is achieved through the use ofdense-walled geometric shapes which are resistant to small particleerosion. Abradability is likewise achieved through the introduction ofcourse (more than 100 microns), closed porosity. The simultaneousoptimization of both erosion resistance and abradability is achievedthrough judicious selection of the values and scale of closed porosity,hollow sphere size & wall thickness. The contribution of the matrix 34is primarily in the mechanical integrity of the structure (strength andelastic constants).

Another example of a material made by the method of this invention,shown ideally in FIG. 3, is a close packed array 40, within the segmentenclosed by the dotted lines, having generally contacting, mostlycontinuous, first layer A, mostly continuous second layer B, shown herefor sake of simplicity as three clusters, and a mostly continuous toplayer, here shown as only two black spheres C, again for clarity. Thisembodiment has almost universal chain formation in three dimensions,providing a high level of constrained stabilized uniform sphericalporosity. That is, the chains prevent collapse and shrinking of thesystem at temperatures approaching 1700° C. Even though most of thelayer B and top layer C spheres are not shown in FIG. 3, it is easy tosee how this invention's 50 vol. % to 90 vol. % hollow shape, herehollow sphere configuration, allows minimizing the binder matrix spaces34. Providing an array, as closely packed as that shown in FIGS. 2 and3, where the matrix spaces 34 are essentially filled, requires aspecialized method of packing and impregnation, as will be detailedlater.

By “substantially close packed” is mean the type array shown in FIGS. 2,3, and 4, where the coordination number, defined previously, is greaterthan or equal to 1. However, some randomness is desired for maximumfracture toughness, strength and flexibility. FIG. 3 shows two sets ofsites for the spheres C of the third layer. A staggered layering asshown by line 44 among spheres A, B, and C, provides a hexagonal closepacked array partly shown. A straight layering as shown by line 46 amongspheres A, B, and C provides a face centered cubic array.

Referring now to FIG. 4, which more clearly illustrates one product ofthe method of this invention, hollow spheres 50, having walls 52, areshown, substantially close packed with, optional smaller, embedded,hollow shapes, such as hollow spheres 54, as well as matrix bindermaterial 56 disposed between the larger hollow spheres 50. Voids 58 arealso shown. The hollow ceramic spheres 50 are manufactured such that thesphere walls are near 70% to 100% of theoretical density, preferablynear 90% to 100% of theoretical density (0% to 10% porous). For gooderosion resistance, the wall thickness is preferably between about 100micrometers to 400 micrometers, depending on sphere diameter. The hollowceramic spheres uniquely control the dimensional stability of thematerial system 60 and inhibit gross volumetric shrinkage due tosintering of the matrix—regardless of the matrix binder materialselected. The hollow spheres are also critical in establishing theunique macro- and microstructure of the material 60 and in controllingits unique behavior, both thermally and mechanically. The level ofclosed macroscopic porosity within the material system 60 is defined bythe overall size of the hollow ceramic spheres, the wall thickness ofthe spheres, and their packing arrangement within the structure. Thebinder that interstitially bonds the hollow ceramic spheres together mayalso contribute a secondary role to these properties depending on themechanical and thermal properties and the amount of binder materialsused. The structure of the material system 60 imparts uniquecombinations of properties including, for gas turbine applications,excellent erosion resistance, insulating properties, and abradability inan optimized combination not achieved by conventional means.

The material system 60, shown in FIG. 4, is made by means of the methodof this invention with closed macroscopic porosity, via the use ofhollow ceramic spheres (or similar geometric shapes) of size rangesbetween 200 micrometers diameter to 5000 micrometers diameter, which areindependently formed and subsequently bonded together to form amacroscopic infrastructure. The bulk density of these spheres 50themselves is anywhere between 0.1 and 0.9 of theoretical, that is 10%to 90%, taking into account the internal porosity, and depending uponthe needs for each high temperature application. The close-packed,contiguous structure defines and controls the thermal and mechanicalproperties of the system 60 and maintains dimensional stability of thestructure. Coordination numbers for the sphere packing can range from 1to 14, but preferably, the coordination number of substantially all ofthe hollow shapes is from 5 to 12, and even more ideally from 5 to 8 forgas turbine coating applications. As mentioned previously, some degreeof randomness is preferred for maximum fracture toughness and strength.However, idealized packing arrangements and high coordination numbers inthe 8 to 14 range, as shown in FIG. 3, may be preferred forstiffness-driven applications such as cores for sandwich structures.

It is critical that the spheres 50 be separately formed and stabilizedand then used as such in this method vs. their being formed in-situ. Theindividually formed and bonded spheres impart unique properties to thematerial system 60. Contact between dense-walled spheres is not overlyintimate due to the binder and possibly smaller included spheres—thusallowing crack deflection and some degree of toughening of the material.Forming the spheres separately allows the stabilization of the spheresto a much higher temperature than otherwise possible. In-situ formedvoids, inevitable in most coating operations, are generallyinterconnected, thus increasing the overall size of critical defects andweakening the structure. By using independently formed hollow spheres,substantially all large voids 50 within the hollow spheres are separatedby at least 2× the sphere wall thickness, as shown, for example, atpoint 62 in FIG. 4. It is also desirable that small voids not beinterconnected, but separated as at point 62.

The ceramic hollow spheres such as 50 in FIG. 4 will typically have awall thickness-to-radius ratio (“t/r” ratio) of between 0.05 to 0.50.Depending upon the application, this “t/r” ratio can vary, for example:for lightweight insulation where erosion is not critical (or isaccommodated), t/r in the lower end of this range is desirable; forinsulating or abradable coatings, that is, in a gas turbine, whereerosion is a concern, t/r between 0.1-0.4 is preferable; for very strongor erosion resistant materials, the higher end of the t/r range isdesirable.

For many applications, the absolute value of the wall thickness iscritical to achieving adequate erosion resistance. Therefore, the t/rand overall diameter of the spheres must be considered. For example, ifa 200 micrometer wall thickness is required for erosion resistance, andthe overall bulk density of the material system is defined byabradability requirements, that is, about 60%, this helps narrow downthe range of sphere sizes possible (other variables include spherepacking density and matrix density). Wall thickness will generally rangefrom about 0.05 mm (50 micrometers) to 5.0 mm (500 micrometers).

The shape of the hollow particles is ideally spherical, for ease ofmanufacture and for attaining isotropic properties. However, othersimilar shapes can be readily made and incorporated in like manner andperhaps introduce certain optimized properties, for example, the shapescan be hollow elongated spheroids or needlelike shapes either randomlyoriented or preferentially oriented parallel or perpendicular to thesubstrate surface and having aspect ratios less than 5-to-1 and lengthsbetween 200 micrometers and 5000 micrometers. Hollow ellipses or otherirregular spheroids can be made and indeed are within the normal rangeof sphere manufacture. Mixtures of spheres, spheroids, low aspect ratiocylinders and other shapes are also natural extensions for use in themethod of this invention and, in fact, at least one manufacturingprocess for hollow spheres also produces hollow, long needle structures.While the invention involves a method of making a material system, it isimportant to recognize the unique properties and parameters of thatsystem, which are accomplished by the manufacturing techniques whichwill be detailed shortly.

Overall bulk density of the entire material system made using the methodof this invention, including the sphere density, their packingarrangement, and the matrix/filler/binder material is generally in therange of 0.10 to 0.80 of theoretical density, depending on theapplication. For the example of turbine engine coatings for eitherinsulation or abradability (or both), the range of overall density ofthe material system and its makeup can vary over a wide range. Bycontrolling the bulk density, that is, sphere size, sphere wallthickness and binder density) of the material system, the properties canbe optimized for erosion resistance and/or abradability. The best rangefor abradable coatings is 30% to 80% theoretical density. The best rangefor erosion resistance is from about a 0.3 to 0.5 t/r within the 30% to80% range.

Note that while FIGS. 2, 3 and 4 show cases of regular packing ofuniformly sized spheres, the packing of the spheres is not limited toeither form or packing nor is it limited to uniformly sized spheres, noris it limited to any kind of regularity of structure (random packing ismore the norm and is allowable so long as the at least substantially“close-packing” criteria is met). Non-uniform sphere sizing may bedesirable to achieve higher sphere packing densities.

Sphere walls must be over 70% dense, but are preferably near theoreticaldensity (90% to 100% of theoretical density) to maintain thermalstability over the widest range of temperatures. The high density of thesphere walls imparts excellent erosion resistance and controls thethermal and mechanical behavior of the system. The manufacturingtemperature of the hollow spheres is well in excess of the intended usetemperature of the material system, for example, mullite (3Al₂O₃.2SiO₂)hollow spheres can be manufactured at 1750° C., rendering them inert andstable in a material system operating indefinitely at 1600° C. to 1700°C. Separately forming and stabilizing the spheres to high temperaturesensures the thermal and dimensional stability of the system at futurehigh temperature operating ranges up to 1700° C. and possibly beyond.The hollow ceramic spheres, rods, etc. are bonded togetherinterstitially by a ceramic matrix material to form a contiguous andself-supporting structure. The matrix material itself and theinterconnected network of spheres both form contiguous structures in theclaimed material. The volume content of the matrix material can varyfrom near zero to completely filling in the interstitial space betweenthe hollow shapes. Preferably the matrix constitutes a minimum of 10% ofthe interstitial space between the hollow shapes for all coordinationmembers. The matrix content and density are tailored to achieve thedesired properties for the specific application, taking into account:the desired bond strength between hollow shapes; the overall bulkdensity required for abradability purposes; the individual and packingdensities of the hollow shapes; permeability requirements; overallmechanical strength of the system; overall thermal conductivityproperties desired; and mass considerations (for example, for flightapplications). The matrix may or may not contain filler or reinforcingmedia, including but not limited to, smaller hollow spheres or othergeometric shapes, powders, particles, platelets, and whiskers or choppedfibers or other discontinuous fibrous materials. In the case ofthick-walled shapes where t/r is greater than 0.25, it may beadvantageous to minimize the amount of matrix in the system—so long asthe bond strength and other criteria are met. A very strong structure,particularly in compression, can be achieved with very little matrixaddition.

The composition of the ceramic hollow shapes can be any oxide ornon-oxide ceramic material including (but not limited to) those shown inTable 1 below: TABLE 1 OXIDES CARBIDES NITRIDES Alumina, Silica SiC, WC,NbC Si₃N₄, TiN Mullite, Zirconia TaC, HfC, ZrC SiCN Zircon, YAG, TiCYttria Ceria, Hafnia, BerylliaThe ceramic matrix material may be either of an oxide based or anon-oxide based composition, including (but not limited to) thecompositions also shown in Table 1 above.

Typically, high temperature, stable ceramic particulate materials areused in the binder system for the material system. The purpose of thesefillers may be to add density to the matrix (without necessarily addingstrength), add strength to the matrix, add toughness to the matrix,either via reinforcing or residual stress management, or improve thevolumetric yield of matrix infiltrates (cost savings). Typically, theparticulate material in the slurry-based binder may be of thecomposition but not limited to those in Table 2 below, and typicalbinders are listed in Table 3 below. TABLE 2 TABLE 3 PARTICULATE BINDERMullite with Aluminosilicate/ Aluminumphosphate Alumina withAluminumphosphate/ Aluminumoxychloride Zirconia withAluminumorthophosphate Hafnia with Aluminumorthophosphate Yttria withAluminumorthophosphate Yttrium Aluminum Garnet withAluminumorthophosphate (YAG) Ceria with Aluminumorthophosphate SiliconCarbide or with Polycarbosilane Silicon Nitride Hollow Shapes of theAbove with All Binders Listed AboveThese materials are slowly mixed together, usually with deionized water,to allow good dispersion. An acid, such as nitric acid, may be added tomaintain the pH of the slurry infiltration solution in the range ofapproximately 3 to 4.

Referring now to FIG. 5, a diagram is shown of the method allowingfabrication of such structures as shown in previously discussed FIGS.2-4. In the method of this invention, a “chamber” which is meant toinclude press or mold having a top, bottom and sides, or a similarapparatus, is provided to initially contain either the geometric shapesfirst or the binder first. In one case, shown by the dotted lines, thegeometric shapes are placed into a chamber—step (2 a), the chamber isclosed—step (2 b), preferably air is evacuated—step (2 c), thereafterthe binder, filled or unfilled, is fed into the evacuated chamber toimpregnate the geometric shapes—step (2 d), which shapes aresubstantially close packed, usually as required for the materialdesired. Usually, a low vacuum is used initially, followed by a higherlevel of vacuum, to insure complete impregantion of the hollow spheres.For example, the vacuum can start at 1 inch (2.54 cm) Hg and be raised,over a period of several hours, to as high as 35 inches (89 cm) Hg.Total vacuum impregnation may take ten to fifteen hours.

In another case, multiple steps are combined, where the binder is placedin the chamber, after which the shapes are inserted and left to settle,and optionally vibrated into a close packed array; or originally slowlystacked as such an array in the binder—all step (2) shown by acontinuous line in FIG. 5. In the first instance (using steps 2 a-2 d),which is preferred, close packing of the shapes in the array is of primeimportance since the shapes are stacked first, before binder is applied.In the second instance (step 2 with continuous lines), complete fillingof void spaces within the array is of prime importance since binder maybe fed into the chamber first. In both cases there will be goodpermeation and penetration of the binder into the void spaces. Thebinder permeated packed array—no mater how accomplished, is thendried—step (3) followed by heating—step (4) and possibly sintering at astepped temperature rate—step (5) and, optionally, binding to asubstrate—step (6). The entire chamber can be heated up to about 80° C.,with the impregnated microspheres in place, as an initial heating stepto remove excess water during step (3).

To insure that the impregnated microsphere body will not crumble, thechamber with the body intact can be heated to about 400° C. beforeremoving the body from the mold. After the body is removed, it can befurther heated, in steps of 2° C. to 10° C. per minute, to 1000° C., toform a secure, unitary structure. To form a true refractory version, thebody can be further heated, in steps of 3° C. to 10° C. per minute, toabout 1600° C. and held for approximately four to five hours. Ifdesired, the unitary body can also be vacuum infiltrated with a ceramicbinder, such as aluminum hydroxyl chloride, with a stepped vacuum up toabout 35 inches (89 cm) Hg, followed by heating and firing attemperatures ranging from 1200° C. to 1600° C.

The method of this invention goes beyond phosphate bonding of ceramichollow spheres using aluminum phosphate and controlled capillary dryingof slurry based components to make simple two-dimensional type coatingsthat could be bonded to a substrate of relatively planar components.This invention is projected for use in complex 3D components such asvane airfoils and combustor liners. This invention provides for theapplication to complex 3D shapes because it employs alternate binders tobond together the ceramic spheres and filler powders. Specifically, theprocessing is not based on capillary drying but is rather based on aprocess of impregnation, preferably under vacuum. The mold forms usedcan be of any required shape, which means that complex shape forms ofthese coatings can be produced. This process is more controllable andcan also be tailored to provide different coating structures to suitrequirements such as erosion resistance and abradability.

In essence, the process of manufacturing via this invention is based ona process of vacuum impregnation, preferably using an inner and an outermold as shown in FIG. 6. The inner shell 82 of the chamber 80 isconnected to a vacuum system 84 capable of producing pressures to atleast 30 mbar. The outer mold 86 consists of a rigid mold shell throughwhich the binder slurry 88 can enter and pass and slowly infiltratethrough the already packed spheres 50. Of course, for example, other lowprofile cylinder shapes or the like could also be used. As is generallyshown, the slurry passes through an opening in the top of mold 86, toadditional openings in the bottom part of mold 86, and then throughspheres 50. At the top surface of the spheres, a porous layer 90 such asplastic meshing is applied to allow mold separation after pressing andfilling. The inner mold 82 also consists of a rigid former 92 throughwhich extracted liquid can be removed, as shown by arrow 94, as a resultof vacuum impregnation of the particles. In addition to the plasticmeshing on this side of the mold, an additional filter layer 96 isrequired that can effectively prevent any fine particles 54 in FIG. 4,in the slurry from passing through the inner mold. This is typically afilter that does not allow particles 54 to pass through, but does allowthe liquid medium to pass through and to go into the vacuum system sothat it can be collected. The porous layer 96 that provides for easyseparation is plastic based, is typically less than 0.5 mm thick and canbe removed easily after infiltration or during partial firing of theentire assembly. The filter 96 is typically made of paper and is lessthan 0.25 mm thick and will burn away during the firing process leavingno residue.

In operation, impregnation of the spheres 50 is achieved preferablyusing a water based slurry 88 that can enter through single or pluralopenings 98. The slurry may consist of a mixture of small particulatesand binders, the function of which is to pack as effectively as possiblein the spaces between the larger sphere's or cylindrical shape's outerwalls. The goal of the impregnation is to fill the interstices of thehollow sphere packed structure with small filler particles after drying.The water (or other specified liquid) is a carrier medium thattransports the powder particles from outside the structure into theinterior of the hollow sphere compact. The carrier is then removed bythe vacuum 84, leaving the solid particles and binder to fill the outersphere spaces. The amount of slurry required can be calculated as afunction of the available intersphere volume. Excess is always preferredto ensure complete filling.

Particle size of any impregnated filler particle can be varied to effectthe appropriate packing density required around the larger particles 50.A typical example of this combination could be coarse mullite3Al₂O₃.2SiO₂) and fine alumina (Al₂O₃). The particle size ratio betweenlarge to small particles should be in the range of 8:1 to 25:1,preferably 10:1 to 15:1. When very small particles are used (5micrometers or less), nitric acid may be added to the slurry to enhanceseparation of the particles in order to provide better rheologicalproperties for more effective infiltration to take place.

As mentioned previously, after impregnation and drying, the body (ingreen form) may be detooled or partially detooled and dry fired atintermediate temperatures of from about 400° C. to 600° C. to impartsome green strength. Subsequently, the green casting may be furtherinfiltrated with a liquid-based binder. This may be completed eitherunder atmospheric pressure or vacuum, depending on the viscosity of thebinder. A number of liquid binder solutions can be used to formeffective binding of the system. These include monoaluminum phosphate,aluminum hydroxyl chloride and ceramic sols that generate alumina,silica, yttria or zirconia solids. All of these binders dictatedifferent and specific firing schedules. Alternately, a highertemperature firing of the green form can be used to sinter the structuretogether. This latter will give the most refractory form of thematerial, but the product will be more brittle. This factor may beimportant if finish machining is required. It is, however, the intentionof this approach to manufacture the coating segments to near net shapeand therefore minimize any machining requirements.

Potential applications of this method are to manufacture an insulatingcoating which can be used on semi-structural ceramic matrix compositecomponents for gas turbines such as transitions, combustor liners, etc.,and for insulating coatings for use on structural ceramic matrixcomposite components such as vanes. Other applications for the materialsystem of this invention may include making materials for application ascombustor liners (can, annular, and can-annular configurations),transition ducts, static airfoils and platforms (vanes), seals (bothblade tip and interstage), and virtually any static surface exposed to ahot gas path. Aerospace applications include aircraft hot gas (engineexhaust) impinged structures and surfaces; thermal protection systems(TPS) for aerospace vehicles (hypersonic or re-entry protection); stiff,lightweight panels or structures for space systems (satellites,vehicles, stations, etc.), etc. Diesel or other ICE applications includecylinder liners, exhaust ports, header liners, etc.

EXAMPLE

In manufacturing a 10 cm×10 cm×2 cm block of the material system of thisinvention, the following constituents were used: 400 g of 10 micronmullite powder, KCM Sintered Mullite from Keith Ceramics; 360 cc ofdeionized water; 70% concentrated nitric acid; 120 g of 0.2 micronalumina powder, AA-61 Alumina from Performance Ceramics Company; and 0.5to 1.5 mm mullite hollow spheres from Keith Ceramics.

To make the slurry infiltration solution, the mullite powder was addedto the water gradually and magnetically stirred for about 10 to 15minutes, followed by a period of about 30 minutes using an ultrasonicprobe, to allow adequate dispersion. Then the concentrated nitric acidwas slowly added, drop by drop, to lower the pH of the solution to 3-4.At this pH, the alumina powder was gradually added, and the pH of thesolution was controlled by adding drops of the concentrated nitric acid,to maintain the pH at, or just below, 4. The materials were mixed forapproximately 30 minutes, to allow the alumina to be finely dispersed inthe mullite slurry solution. The slurry solution was then ready forvacuum impregnation.

To vacuum infiltrate a compaction of the hollow mullite ceramic spheresdescribed above, an apparatus similar to that depicted in FIG. 6 wasused. The enclosure to be infiltrated was filled with hollow ceramicspheres (shown as 50), which were packed as effectively as possible.Here, the chamber was packed with the hollow ceramic spheres using avibrating table to shake the spheres into an optimum packing density.Once the spheres were packed into the open chamber, the tooling wasbolted together and sealed using rubber seals between all matedsurfaces, to ensure an adequate vacuum.

At the vacuum end of the infiltration chamber (shown as 94), a membranewas used which allowed the liquid constituent of the slurry to passthrough, but not the solid constituent, which forms the matrix thatbinds the spheres together. The membrane on the non-vacuum side allowedall constituents of the slurry to pass into the interstices between thepacked hollow ceramic spheres.

The slurry infiltration solution was then applied to the chamber throughthe non-vacuum side and was allowed to saturate the sphere-packedchamber. A minimal vacuum (2.54 cm Hg) was applied, to initiate thematrix packing process. During the next 15 minutes, the vacuum level wasgradually raised to 12.7 cm Hg. The vacuum was maintained at this levelfor 20 minutes. The vacuum was then raised to 17.78 cm Hg and held for afurther 30 minutes. After this period, the vacuum was raised, at 2.54 cmHg per minute, to 30.5 cm Hg and held for a further 10 minutes. Then thevacuum was again raised, at 2.54 cm Hg per minute, to 45.7 cm Hg andheld for a further 30 minutes. (More slurry can be added at this stage,if required.) The vacuum was then raised to about 76 cm Hg at about 7.6cm Hg per minute and held at this maximum vacuum level for about 10hours. After this period, the tooling was dried in an oven at 60° C. toremove any excess water remaining in the system.

The green body was then placed in a furnace with the metallic toolingand fired at gradually-increasing (2° C. per minute) temperatures to400° C. and held at this temperature for 2 hours. After this, the greenbody had sufficient strength to be removed from the tooling and fired,standing alone, at gradually-increasing (2° C. per minute) temperaturesto 550° C. It was held for 1 hour, then the temperature was increased,by 7° C. per minute, to 900° C., and it was again held for 2 hours, toform a unitary structure. Then the structure was cooled, at 10° C. perminute, to room temperature and removed from the oven. At this stage,the body has sufficient strength to be carefully handled.

Alternatively, the body can be fired under controlled conditions (5° C.per minute) to 1600° C. and held for 4 hours, to form a refractoryversion of the structure.

In order to develop full strength, the body structure was infiltrated byaluminum hydroxyl chloride (Keith Ceramics Bonding Agent KCM 2025),acting as a ceramic binding solution. This improved the overall strengthof the structure body. Infiltration of the body occurred as follows. Thestructure body was placed in a vacuum chamber with sufficient bindingsolution to cover the body. A vacuum was slowly applied to the body toremove any entrapped air that might inhibit effective wetting of thebody by the binder solution. The vacuum was applied at the rate of 12.7cm per minute to 50.8 cm Hg, and then further increased to 76.2 cm Hg atthe same rate. When the maximum vacuum was obtained, that level was thenheld for 2 minutes. After this, the system was allowed to return slowlyto atmospheric pressure. The soaked body was then removed and heatedunder a 200-watt lamp for approximately 8 hours, being turnedoccasionally to promote consistent drying through the body. After this,the body was fired to 900° C. at 7° C. per minute and held at thattemperature for 2 hours, then cooled to room temperature at 10° C. perminute. (This cycle can be repeated up to three times, to obtain maximumstrength values.) In the final firing, the temperature was raised to1200° C., at the same rate (7° C. per minute), to complete theprocessing of the body with the added binder.

The present invention may be embodied in other forms without departingfrom the spirit or essential attributes thereof, and accordingly,reference should be made to both the appended claims and the foregoingspecification as indicating the scope of the invention.

1-12. (canceled) 13-15. (canceled) 16-18. (canceled) 19-20. (canceled)21. A material system for use in a high temperature environment inexcess of approximately 1 300° C., comprising: a plurality of generallycontacting dimensionally stable geometric shapes having an oxide basedcomposition, the shapes being close packed with void spaces therebetweensuch that a substantial number of the shapes contact at least 1 adjacentother shape, the dimensionally stable geometric shapes formed at astabilizing temperature that causes the shapes to not sinter to oneanother at a temperature at which the geometric shapes would sintertogether prior to stabilization; and a binder material coating at leasta portion of the geometric shapes, whereby heating the coated geometricshapes to at least 400° C. forms the material system adapted for use inthe high temperature environment in excess of approximately 1300° C. 22.The material system of claim 21, wherein the geometric shapes arehollow, and achieve dimensionally stability by being preheated to atemperature in excess of 1600° C.
 23. The material system of claim 21,wherein the binder material is in a slurry form when used to coat thegeometric shapes. 24-28. (canceled)
 29. A material for use in a hightemperature environment at a use temperature, the material comprising: apacked plurality of geometric shapes defining spaces there between, thegeometric shapes being individually formed at a manufacturingtemperature sufficiently high so that the geometric shapes remain stableand do not sinter together during manufacturing of the material or whenthe material is operated at the use temperature; and a binder materialholding the geometric shapes together.
 30. The material of claim 29,wherein the geometric shapes comprise spheres having sphere walls of70-100% theoretical density.
 31. The material system of claim 21,wherein the binder material comprises an aluminum phosphate basedcomposition.
 32. The material system of claim 21, wherein the geometricshapes are spheres.
 33. The material system of claim 21, wherein thematerial system is used in a combustion turbine engine.
 34. The materialsystem of claim 21, wherein the material system is used with a componentselected from the group consisting of: blade, vane, combustor and shroudseal.
 35. The material of claim 29, wherein the binder materialcomprises an aluminum phosphate based composition.
 36. The material ofclaim 29, wherein the material is used in a combustion turbine engine.37. The material of claim 29, wherein the material is used with acomponent selected from the group consisting of: blade, vane, combustorand shroud seal.